Microstructure and mechanical properties of Mo/DLC nanocomposite films

Mo-doped diamond-like carbon (Mo/DLC) films were deposited on stainless steel and Si wafer substrates via unbalanced magnetron sputtering of molybdenum combined with inductively coupled radio frequency (RF) plasma chemical vapor deposition of CH₄/Ar. The effects of Mo doping and sputtering current on the microstructure and mechanical properties of the as-deposited films were investigated by means of X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), transmission electron microscopy (TEM), Raman spectroscopy, atomic force microscopy (AFM), and nano-indentation. It was found that Mo doping led to increase in the content of sp² carbon, and hence decreased the hardness and elastic modulus of Mo/DLC films as compared with that of DLC films. The content of Mo in the films increased with the increasing sputtering current, and most of Mo reacted with C atoms to form MoC nanocrystallites at a higher sputtering current. Moreover, the Mo-doped DLC films had greatly decreased internal stress and increased adhesion to the substrate than the DLC film, which could be closely related to the unique nanocomposite structure of the Mo-doped films. Namely, the Mo/DLC film was composed of MoC nanoparticles embedded in the cross-linked amorphous carbon matrix, and such a kind of nanostructure was beneficial to retaining the loss of hardness and elastic modulus.     

Structure of the silver containing diamond like carbon films: Study by multiwavelength Raman spectroscopy and XRD

In the present study structure of silver containing diamond like carbon (DLC:Ag) films deposited by reactive magnetron sputtering was investigated by X-ray diffractometry (XRD) and multiwavelength Raman spectroscopy. In the case of the DLC:Ag films containing low amount of silver, crystalline silver oxide prevails over silver. While at higher Ag atomic concentrations formation of the silver crystallites of the different orientations was observed. Surface enhanced Raman scattering (SERS) effect was detected for high Ag content in the films. For UV excited Raman spectra sp³ bonded carbon related Raman scattering T peak at ~ 1060 cm^− 1 was detected only for the films with the highest amount of silver (34.3 at.%). The dependence of the Raman scattering spectra parameters such as position of the G peak, G peak full width at half maximum (FWHM(G)), D/G peak area ratio on Ag atomic concentration in DLC:Ag film as well as Raman scattering spectra excitation wavelength were studied. The dependence on Ag amount in film was more pronounced in the case of the Raman scattering spectra excited by higher wavelength laser beam, while in the case of the spectra excited by 325 nm and 442 nm laser beams only weak dependence (or no dependence) was observed. Overall tendency of the decrease of the dispersion of the G peak with the increase of Ag atomic concentration was found. Thus sp³/sp² bond ratio in DLC:Ag film decreased with the increase of Ag atomic concentration in the films.     

Electrochemical characterization of diamond like carbon thin films

Diamond-like carbon (DLC) thin films were deposited from pure graphite target by DC magnetron sputtering method. Experimental parameters, i.e., substrate temperature and negative bias voltage, have been changed to finely tune the chemical bonding property (sp²/sp³) of the as-deposited DLC films. The as-deposited DLC films were characterized as anode materials for Li–ion batteries and special attentions were paid to the effects of sp²/sp³ ratio on the electrochemical properties of the DLC films. The results indicated that a high fraction of sp² bonding in the DLC films is preferred for high lithium storage capacity, flat and low charge voltage plateau, and long cycling retention.     

Me-DLC films as material for highly sensitive temperature compensated strain gauges

In technical applications strain gauges are widely used. Apart from conventional polymer foil based strain gauges that are glued to the work piece surface, sputtered strain gauges are already commercially used in special applications. Those sputter strain gauges are typically made of NiCr alloy and the sensor layer is as sensitive to strain as the ones used in the glued strain gauges with a gauge factor of 2, but neglecting problems of creeping and swelling of the involved polymer materials. Diamond-like carbon (DLC) films offer significantly higher strain sensitivity, but usually they are also very sensitive to temperature effects. Using metal doped diamond-like carbon (Me-DLC), higher strain sensitivity than conventional metal based systems, in combination with thermal compensation, is possible. The influence of different process parameters on the gauge factor and temperature coefficient of resistance (TCR) of DLC and Me-DLC films produced in industrial sputtering systems was investigated. Gauge factors up to 13 in combination with a high negative TCR in the range of a few thousand ppm/K were reached with sputtered DLC films. The substrate bias voltage in particular showed a strong influence on the resulting gauge factor of the films. For Me-DLC films different deposition methods (dc and rf sputtering) and various doping metals (Ag, Ni, Ti, and W) were investigated. Using dc sputtering of the Me-DLC films only Ni-DLC showed gauge factors slightly higher than 2. Furthermore, only for Ni-DLC zero crossing of the TCR was observed by variation of the metal content. Using rf excitation especially Ni-DLC films showed gauge factors exceeding values of 15 in combination with a TCR close to zero.     

Formation and characterization of DLC:Cr:Cu multi-layers coating using cathodic arc evaporation

Chromium and copper-doped diamond-like carbon (DLC:Cr:Cu) films were deposited on SKH 51 tool steel. We have prepared multilayers of DLC:Cr and DLC:Cu by cathodic arc evaporation process using chromium (Cr) and copper (Cu) target arc sources to provide Cr and Cu in the DLC. Acetylene reactive gases were also activated at a pressure of 5 mTorr to 25 mTorr and a temperature fixed at 180 °C to provide the DLC. The resulting DLC:Cr:Cu film contained Cr_xCu_y as well as Cr_xC_y nanoparticles vital for the film mechanical properties. The crystal structure was investigated using X-ray diffraction (XRD) and transmission electron microscopy, while the surface morphology and chemical composition were studied by field emission scanning electron microscopy and X-ray photoelectron spectroscopy. The process parameters were compared by studying the various mechanical properties of the films such as microhardness and residual stress. The result of this process enhanced the DLC:Cr:Cu composite coatings for high toughness and lower friction coefficient (0.08). The profiles of sp³/sp² (XPS) ratios corresponded to the change of microhardness profile by varying the pressure of the hydrocarbon gases (C₂H₂).     

Blood compatibility of La2O3 doped diamond-like carbon films

La₂O₃ doped diamond-like carbon films (DLC) with different concentration were deposited by using Radio-Frequency magnetron sputtering. The microstructure and surface properties of DLC films were characterized by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and contact angle test. The blood compatibility of the samples was evaluated by tests of platelet adhesion. Results show the sp²-bonded C content increases with increasing of La₂O₃ concentration doped. A remarkable decrease of platelet adhered on the surface of the La₂O₃ doped DLC films was observed comparing to the Chrono flex used in clinical application, suggesting that La₂O₃ doped DLC is able to enhance its blood compatibility. The mechanism of hemocompatibility of doped films was discussed. Our results demonstrate that La₂O₃ doped DLC films are potentially useful biomaterials with good blood compatibility.     

Effects of thermal annealing and Si incorporation on bonding structure and fracture properties of diamond-like carbon films

The effects of thermal annealing and Si incorporation on the structure and properties of diamond-like carbon (DLC) films were investigated. As-deposited DLC film (DLC) and Si incorporated DLC film (Si-DLC), both with and without thermal annealing, were analyzed for bonding structure, residual stress, film thickness, elastic modulus and fracture properties using Raman spectroscopy, wafer curvature, nanoindentation, four-point bend fracture testing, and X-ray photoelectron spectroscopy (XPS). Raman spectroscopy clearly showed that thermal annealing of DLC films promotes more sp² bonding character, whereas Si incorporation into the films promotes more sp³ bonding character. Interfacial fracture energies, film hardness and elastic modulus, and residual film stress were all found to vary strongly with the degree of sp³ bonding in the DLC film. These changes in mechanical properties are rationalized in terms of the degree of three dimensional inter-links within the atomic bond network.     

Microstructure,mechanical property and thermal stability of diamond-like carbon coatings with Al,Cr and Si multi-doping

In this paper, AlCrSi atoms were co-doped into DLC coatings by using a high power impulse magnetron sputtering combining with an anode-layer linear ion beam. The doped AlCrSi contents were controlled via adjusting the Ar fraction in the sputtering gas mixture of Ar and C₂H₂. The influences of the AlCrSi multi-doping on the composition, microstructure, residual stress, mechanical property and tribological behavior of the as-deposited DLC coatings were studied systemically by using EDS, XPS, TEM, stress-tester, nanoindentation and ball-on-plate tribometer as a function of the Ar fraction. The thermal stability of the coatings was also researched by a vacuum heat treatment with various temperatures. The results show that the carbide former Cr preferred to form hard carbide components which were conducive to the hardness of the coatings, while the weak carbide former Al dissolved in the DLC matrix as metallic state, which can effectively released the stress of the DLC coatings. The doped Si would bond with sp²-C to form sp³ CSi, and thus maintained the sp³-C structure stability and improved the thermal stability of the coatings. Accordingly, the DLC coatings with AlCrSi multi-doping not only exhibited relatively low residual stress and high hardness, but also showed a high thermal stability over 500 °C. It was believed that the AlCrSi multi-doping may be a good way for improving the comprehensive properties of the DLC coatings.     

Structure and mechanical properties of oxygen doped diamond-like carbon thin films

In this study, structure and mechanical properties of doped diamond-like carbon (DLC) films with oxygen were investigated. A mixture of methane (CH₄), argon (Ar) and oxygen (O₂) was used as feeding gas, and the RF-PECVD technique was used as a deposition method. The thin films were characterized by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy (RS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and a combination of elastic recoil detection analysis and Rutherford backscattering (ERDA-RBS). Nano-indentation tests were performed to measure hardness. Also, the residual stress of the films was calculated by Stoney equation. The XPS and ERDA-RBS results indicated that by increasing the oxygen in the feeding gas up to 5.6 vol.%, the incorporation of oxygen into the films' structure was increased. The ratio of sp² to sp³ sites was changed by the variation of oxygen content in the film structure. The sp²/sp³ ratios are 0.43 and 1.04 for un-doped and doped DLC films with 5.6 vol.% oxygen in the feeding gas, respectively. The Raman spectroscopy (RS) results showed that by increasing the oxygen content in doped DLC films, the amount of sp² CC aromatic bonds was raised and the hydrogen content reduced in the structure. The attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) confirmed the decrease of hydrogen content and the increase the ratio of CC aromatic to olefinic bonds. Hardness and residual stress of the films were raised by increasing the oxygen content within the films' structure. The maximum hardness (19.6 GPa) and residual stress (0.29 GPa) were obtained for doped DLC films, which had the maximum content of oxygen in structure, while the minimum hardness (7.1 GPa) and residual stress (0.16 GPa) were obtained for un-doped DLC films. The increase of sp³ CC bonds between clusters and the decrease of the hydrogen content, with a simultaneous increase of oxygen in the films' structure is the reason for increase of hardness and residual stress.     

A diamond-like carbon film as a self-alignment layer for LCDs

Diamond-like carbon (DLC) films without H deposited with a DC magnetron in-line sputtering system have shown sufficient self-alignment properties towards liquid crystals (LC). The DLC film was successfully used as an alignment layer for LC without any alignment processes such as rubbing or atomic beam bombardment or UV irradiation. From the observations of the test cells, the LC director was aligning parallel to the substrate movement direction of the in-line sputtering system. The alignment property of the DLC films has been demonstrated by a contrast ratio value of close to 200. It appears that DLC film may have anisotropic structure that is interacting with LC to align.     

Enhancement of adhesion strength and corrosion resistance of nitrogen or platinum/ruthenium/nitrogen doped diamond-like carbon thin films by platinum/ruthenium underlayer

A platinum/ruthenium (PtRu) underlayer was grown on highly conductive p-Si (100) substrates, on which nitrogen doped diamond-like carbon (N-DLC) thin films without or with incorporation of Pt and Ru (PtRuN-DLC) were deposited, both via a DC magnetron sputtering system. The effect of PtRu underlayer on the bonding structure, surface morphology and adhesion strength of the N-DLC and PtRuN-DLC films was investigated using X-ray photoelectron spectroscopy (XPS) and micro-Raman spectroscopy, atomic force microscopy (AFM) and micro-scratch testing, respectively. The effect of the PtRu underlayer on the corrosion performance of these films in a 0.1 M HCl solution was diagnosed using electrochemical impedance spectroscopy (EIS). Although the incorporation of Pt and Ru into the N-DLC films promoted sp² sites in the films via metal-induced graphitization, the PtRu underlayer along with the incorporation of Pt and Ru in the N-DLC films could enhance the charge transfer resistance of the films, indicating the increased corrosion resistance of the films.     

Reactive sputter-deposition of oxygenated amorphous carbon thin films in Ar/O2

Oxygenated amorphous carbon thin films were deposited by DC magnetron sputtering using various argon and oxygen process gas mixtures. The X-ray diffraction data indicated that the predominantly amorphous films had more defined peaks with a higher partial pressure of oxygen. Results indicated that use of oxygen in the working gas enhanced the crystalline nature of the films. Scanning electron and atomic force microscopy revealed that the surface roughness and film topography differed with the oxygen process gas variations. X-ray photoelectron spectroscopy revealed increased surface oxygen content with higher oxygen concentration in the working gas. Raman spectroscopy results suggested that the increased oxygen in the films may have led to a higher percentage of sp³-bonded carbon atoms. The growth rate (deposition rate) of the films decreased as the amount of oxygen increased. This decreased deposition rate was associated with an oxygen etching of the film.     

Effect of sputtering power on piezoresistivity and interfacial strength of SiCN thin films prepared by magnetic sputtering

SiCN ceramics show large potential in high temperature pressure sensors with excellent stability up to 1000 °C, as it is changeling for the most of the existing pressure sensors to work stably at a temperature above 600 °C. However, bulk SiCN ceramics are not compatible to microelectronic processing and exhibit slow response due to viscoelasticity, it is necessary to propose alternative method to prepare SiCN functional structures. In this work, SiCN piezoresistive thin films are prepared by magnetron sputtering, and the influence of sputtering power on their piezoresistive properties and interfacial strengths are studied. The gauge factors of SiCN films range from 2786 to 4714 at various sputtering powers, which are significantly higher than the range from 46 to 1105 for existing piezoresistive thin films. Upon an optimal sputtering power of 75 W for silicon nitride target, the obtained SiCN sample show the largest gauge factors in a large range from 0.5 to 3.4 MPa. Furthermore, the SiCN thin films present high critical loads up to 36.5 N in scratch tests and indicate strong interfacial adhesion with substrate. This work provides an important reference for developing SiCN-based MEMS pressure sensors.     

CuO thin films produced for improving the adhesion between Cu and Al2O3 foils in a direct bonded copper (DBC) process

The direct bonded copper (DBC) process was carried out between Cu and Al₂O3 foils and CuO thin films were grown on the surface of Cu foils to reduce the defects produced by the DBC on the surface. CuO thin films were synthesized using a magnetron sputtering system, employing a target of Cu with 99.99% of purity and substrates of Cu foils. The discharge atmosphere for the films growth was (Ar + O₂). Once the coatings were grown, coated and uncoated Cu foils were joined at both sides (one on the top and the other at the button) of the alumina foil using the traditional direct bonded process. The Atomic concentration, chemical composition and bonding configuration of both cases were studied by X-ray photoelectron spectroscopy (XPS), finding Metallic Cu, Cu₂O and Cu–O bonds; furthermore, the atomic concentration analysis showed that coated Cu foil exhibited lower oxygen percentage, compared with uncoated one. The study of the surface defects was carried out using scanning electron microscopy (SEM) showing that the Al₂O3 ceramic was better pasted with the Cu foil including the CuO thin film.     

Preparation of diamond like carbon thin films above room temperature and their properties

Diamond like carbon (DLC) thin films were deposited on p-type silicon (p-Si), quartz and ITO substrates by microwave (MW) surface-wave plasma (SWP) chemical vapor deposition (CVD) at different substrate temperatures (RT ∼ 300 °C). Argon (Ar: 200 sccm) was used as carrier gas while acetylene (C₂H₂: 20 sccm) and nitrogen (N: 5 sccm) were used as plasma source. Analytical methods such as X-ray photoelectron spectroscopy (XPS), FT-IR and UV–visible spectroscopy were employed to investigate the structural and optical properties of the DLC thin films respectively. FT-IR spectra show the structural modification of the DLC thin films with substrate temperatures showing the distinct peak around 3350 cm^− 1 wave number; which may corresponds to the sp² C–H bond. Tauc optical gap and film thickness both decreased with increasing substrate temperature. The peaks of XPS core level C 1 s spectra of the DLC thin films shifted towards lower binding energy with substrate temperature. We also got the small photoconductivity action of the film deposited at 300 °C on ITO substrate.     

Changes in chemical bonding of diamond-like carbon films by atomic-hydrogen exposure

We have deposited unhydrogenated diamond-like carbon (DLC) films on Si substrate by pulsed laser deposition using KrF excimer laser, and investigated the effects of atomic-hydrogen exposure on the structure and chemical bonding of the DLC films by photoelectron spectroscopy (PES) using synchrotron radiation and Raman spectroscopy. The fraction of sp³ bonds at the film surface, as evaluated from C1s spectra, increased at a substrate temperature of 400 °C by atomic-hydrogen exposure, whereas the sp³ fraction decreased at 700 °C with increasing exposure time. It was found that the sp³ fraction was higher at the surfaces than the subsurfaces of the films exposed to atomic hydrogen at both the temperatures. The Raman spectrum of the film exposed to atomic hydrogen at 400 °C showed that the clustering of sp² carbon atoms progressed inside the film near the surface even at such a low temperature as 400 °C.     

The origin of conductivity in ion-irradiated diamond-like carbon – Phase transformation and atomic ordering

Focused ion irradiation of insulating diamond-like carbon (DLC) films is a well-recognized approach to write defined nanostructures with drastically changed properties compared to the unexposed matrix. In particular, the electrical conductivity of the film areas that are irradiated increases by several orders of magnitude. Furthermore it is known that the conductivity increase is directly related to the irradiation-induced sp³–sp² rehybridization. This experimental work shows in detail that ion-induced microstructural ordering of the carbon atom arrangement far beyond the sp³–sp² conversion saturation is an important microscopic mechanism for the alteration of physical properties, including an increase in the conductivity. The atomic ordering correlates with the local energy density deposited during the ion impact. Thus the ion-induced phase transformation of DLC is proposed to comprise a rehybridization stage, caused by nuclear collisions, and a rearrangement stage (graphite-like ordering) that is thermally driven by the ion impact. These conclusions are based on in-depth investigations of amorphous DLC films that were locally irradiated by a number of ion species employing several temperature regimes. The ion irradiation experiments cover a wide range of fluences. X-ray photoelectron spectroscopy, μ-Raman spectroscopy, transmission electron microscopy, and low temperature transport measurements have been applied to characterize the films.     

Characteristics of carbon films prepared by plasma-based ion implantation

A series of carbon films have been prepared by plasma-based ion implantation (PBII) with C on pure Al and Si. Emphasis has been placed on the effect of implanting voltage on the characteristics of these films. The structures of the films were analyzed by X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy. The morphologies were observed by atomic force microscope (AFM). Surface hardness and electrical resistivity were also measured. The results indicate that the characteristics of these films are strongly dependent on the implanting voltage. An implanting voltage threshold value ranging from 3 to 5 kV starts to form a C-substrate transition layer owing to C⁺ ions implanted into the substrate. The transition layer exhibits a gradual change in composition and structure and effectively connects the carbon film and the substrate. Also, an implanting voltage threshold value ranging from 5 to 10 kV starts to form diamond-like carbon (DLC) films. An increasing voltage causes the resultant DLC films to be smoother and more compact. Moreover, Raman spectrum, chemical state of C1s, surface hardness and electrical resistivity all prove an optimum voltage of approximately 30 kV corresponding to the lowest ratio of sp²/sp³.     

Structural characterization of diamond-like carbon films for ultracold neutron applications

We have produced hydrogen-free diamond-like carbon (DLC) films by vacuum arc deposition for use as wall coating material in ultracold neutron (UCN) applications. The sp³ fraction, the main quality factor for DLC used in UCN applications, was varied from 0.4 to 0.9, the coating thickness between 10 nm and 120 nm. The samples were characterized by using X-ray Absorption Near-Edge Spectroscopy (XANES), X-ray induced Photoelectron Spectroscopy (XPS), Laser induced surface Acoustic Waves (LAwave), cold neutron reflectometry and Raman spectroscopy at visible excitation wavelength. We observe reasonable agreement between the different results for film thicknesses below 20 nm. For larger thickness, we find that the surface-sensitive methods XPS and XANES yield smaller sp³ fractions (by up to 20%) than the bulk-sensitive LAwave, being consistent with the assumption of a lower-density surface layer on a nominal-density bulk layer.     

Etching of DLC films using a low intensity oxygen plasma jet

This article describes the characteristics of the etching process of diamond-like carbon (DLC) films using a new plasma system based on an oxygen plasma jet which comprises charged particles and activated neutral species in a range of energies and fluxes suitable for the etching process. This plasma source was used to etch DLC films which were grown on silicon substrates by magnetron sputtering technique. Prior to etching these films were characterized by different methods, namely Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), current×voltage curves and atomic force microscopy (AFM). Etch rates in the range 7.0–25 nm/min were measured for substrates placed at different positions along the axis of the plasma jet. An attractive feature observed in this work was the influence of an axial magnetic field applied to improve the confinement of the plasma stream. An increase by a factor of 3.4 in the etch rate was verified when the magnetic field increased from 2.5 to 6.0 mT. Raman spectra features (line shapes, frequencies and line width) of the etched films were compared with those obtained before etching. The results show that this plasma jet etching is a reliable technique for DLC film processing.